The tribological performance of Si3N4 ball sliding against Ti3SiC2 disc lubricated by lithium-based ionic liquids (ILs) was investigated using an Optimol SRV-IV oscillating reciprocating friction and wear tester at room temperature (RT) and elevated temperature (100°C). Glycerol and the conventional imidazolium-based IL 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (L-F106) were used as references under the same experimental conditions. The results show that the lithium-based ILs had higher thermal stabilities than glycerol and lower costs associated with IL preparation than L-F106. The tribotest results show that the lithium-based ILs were effective in reducing the friction and wear of Si3N4/Ti3SiC2 contacts. [Li(urea)]TFSI even produced better tribological properties than glycerol and L-F106 both at RT and 100°C. The SEM/EDS and XPS results reveal that the excellent tribological endurance of Si3N4/Ti3SiC2 contacts lubricated by lithium-based ILs was mainly attributed to the formation of surface protective films composed of various tribochemical products.